PREPARATION  OF  ORGANIC  ALUMINIUM 
COMPOUNDS  BY  THE  GRIGNARD 
REACTION 

liV 


RALPH  WALDO  POOLER 

B.S.  University  of  Illinois,  1921 


THESIS 

SUBMITTED  IN  PARTIAL  FULFILLMENT  OF  THE  REQUIREMENTS 
FOR  THE  DEGREE  OF  MASTER  OF  SCIENCE  IN  CHEMISTRY 
IN  THE  GRADUATE  SCHOOL  OF  THE  UNIVERSITY 
OF  ILLINOIS,  1922 


URBANA,  ILLINOIS 


Digitized  by  the  Internet  Archive 
in  2016 


https://archive.org/detaiis/preparationoforgOOfogi 


A, 


UNIVERSITY  OF  ILLINOIS 


THE  GRADUATE  SCHOOL 


-1922— 


1 HEREBY  RECOMMEND  THAI'  THE  THESIS  PREPARED  UNDER  MA' 


SUPERVISION  BY Ha34)±L-''laLdo  Fnglep 


ENTITLEDPr_eT)arajtion  of— Qi»gan1.C- 


Gr_ignand  EeacM  on . 


BE  ACCEPTED  AS  FULFILLING  THIS  PART  OF  THE  REQUIREMENTS  FOR 


THE  DEGREE  OF Idaater  of  Solenna- 


CcX/vi?.  jj. 


In  Charge  of  Thesis 


^ Head  of  Department 


Recommendation  concurred  in* 


Committee 


on 


Final  Examination* 


Retjuired  for  doctor’s  degree  but  not  for  master’s 


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CONTENTS 


Pages 

ACKNOWLEDCTvIENT 

I  INTRODUCTION  1 

Purpose  of  Research  1 

Methods  of  Separating  Rare  Earths  nov/  in  Use  1 

Application  to  Priedel  and  Crafts’  Reaction  2 

II  HISTORICAL  AND  THEORETICAL  3 

History  of  Priedel  and  Crafts’  Reaction  3 

Applications  3 

Theories  Advajiced  for  Mechanism  Envolved  3 

Theory  of  Formation  of  Phenyl  Aluminium  Chloride  7 

III  EXPERIMENTAL  9 

Apparatus  9 

Preparation  of  Reagents  10 

Propyl  Magnesium  Bromide  10 

Phenyl  Magnesium  Bromide  10 

Dry  Petroelum  Ether  11 

Aluminiimi  Bromide  11 

IV  CONCLUSION  25 

V  BIBLIOGRAPHY  26 


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ACKNOWLEDGMENT 


This  problem  was  suggested  by  Dr.C.  S.  Marvel 
The  writer  wishes  to  thank  him  for  his  many  sug 
gestions  and  untiring  assistance. 


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1 


I 

I 

INTRODUCTION 


The  study  of  the  action  of  Grignard  reagent,  RM^,  on  aluminium 
chloride  and  bromide  was  suggested  by  the  fact  that  an  analogous  re- 
action using  mercuric  halides  had  been  carried  out  very  successfully 
in  this  laboratory  by  other  workers* 

It  was  noticeable  that  in  all  cases  the  dialkyl  mercury  com- 
pounds were  all  liquids*  Also  by  reference  to  the  literature  it  was 
found  that  the  aryl  and  alkyl  aluminium  compounds  were  also  liquids. 
It  mi^t  be  stated  here  that  the  alkyl  and  aryl  aluminium  compounds 
in  themselves  have  little  interest  but  throu^  the  study  of  these 
compounds,  one  ?/ould  be  able  to  study  the  rare  earth  alkyls*  In 
other  words  the  original  idea  of  this  research  was  to  find  a means  of 
separating  the  rare  earths  from  each  other  by  fractional  distillation 
of  the  alkyl  or  aryl  rare  earth  compounds,  prepared  by  the  action  of 
Grignard ’s  reagent  on  their  chlorides* 

I Since  aluminium  is  in  the  same  group  in  the  periodic  table  and 

j 

I there  is  no  great  difference  in  the  properties  of  these  elements, 

i 

I and  due  to  the  abundance  of  alwninium  and  its  compounds,  it  was  used 

las  a starting  point  for  this  investigation. 

I 

i The  methods^most  commonly  used  for  the  separation  of  the  rare 

I earth  elements  from  one  another  are  of  tv/o  general  kinds:  (1)  Those 

I depending  on  the  difference  in  solubility  of  the  various  salts;  (2) 

1 

i 

f 

! 

i— — I 


2 


and  those  based  upon  the  difference  on  the  basicity  of  elements* 

The  above  mentioned  methods  are  both  wasteful  and  tedious.  So  it 
was  thought  that  fractional  distillation  would  be  quicker  and  easier 
if  a method  could  be  worked  out. 

The  chlorides  and  bromides  of  the  rare  earths  are  easily  pre- 
pared in  anhydrous  state  and  this  point  tends  to  favor  the  use  of 
the  Grignard  reagent  in  preparation  of  alkyl  derivatives.  These 
ilkyl  rare  earths  then  in  turn  could  be  fractional  distilled  and  the 
desired  fractions  collected, 

?/ith  this  aim  in  view  investigation  was  started  and  it  was  at 
once  noticed  that  the  reaction  do  not  go  to  give  the  trialkyl  com- 
poimd  but  appeared  to  form  a compound  of  the  RAlClg  type.  This 
proved  to  be  interesting  because  of  the  fact  it  could  be  used  to  study 
the  mechanism  of  the  Friedel  and  Grafts’  reaction.  Therefore,  the 
work  shifted  to  the  study  of  the  mechanism  of  the  Friedel  and  Crafts’ 
reaction  and  the  greater  portion  of  the  v/ork  was  devoted  to  this  line 


II 


3 


HISTORICAL  AND  THEORETICAL 


The  Priedel  and  Crafts'  reaction,  a reaction  which  has  had  an 
extremely  wide  and  varied  application,  was  discovered  in  1877  by 
C*  Priedel  and  J,  M*  Crafts®*  It  is  connected  more  particularly  witli 
synthesis  of  aromatic  hydrocarbons  but  is  also  used  in  synthesizing 
a variety  of  other  organic  compounds  such  as,  acid  chlorides,  ketones 
aldehydes  and  acids*  I^droxyl  and  amino  groups,  if  present  in  the 
nucleus  must  be  protected  by  converting  the  former  into  an  ether  and 
the  latter  into  an  acetyl  derivative*  Nitro  compounds  do  not  react* 
The  reaction  may  also  be  used  to  produce  internal  condensations  * 

Due  to  the  dehydrating  action  of  anhydrous  aluminium  chloride  under 
some  conditions  it  may  also  prodixje  decomposition.  Pinally  it  may 
accomplish  a transfer  of  carbons  from  one  carbon  atom  to  another 
within  the  benzene  nucleus*  The  active  agent  in  the  reaction  is 
aluminium  chloride.  Perric  chloride  and  zinc  chloride  have  been 
used  to  a lesser  extent* 

Several  theories  have  been  advanced  to  explain  the  various 
changes  produced  by  aluminium  chloride*  The  first  publications®  in 
1877,  offered  a theory  of  the  reaction  based  upon  analogies  with  the 
properties  of  organo-me tallic  bodies.  It  was  supposed  that  all  the 
observed  effects  might  be  explained  by  the  existence,  even  in  small 
proportions  of  an  organo-me  tallic  chloride,  CO-Als,  Clg,  which 
being  constantly  decomposed  according  to  the  equation  and  constantly 


+ RCL 


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renewed,  would  explain  the  contact  action  of  aluminium  chloride. 

This  theory  was  kept  in  view  throughout  subsequent  work  and  was 
strengthened  by  many  new  facts  and  paj?ticularly  by  those  relating  to 
the  readiness  with  which  oxygen-,  carbon  dioxide®,  sulphur  dioxide 
and  cyanogen  are  absorbed  by  the  benzene  compound  with  aluminium 
chloride,  giving  respectively  phenol,  benzoic  acid,  phenyl  mercaptans 
and  diphenyl  sulphide,  phenyl  sulfonic  acid,  and  phenyl  cyanide.  The 
smll  quantity  of  each  of  these  products  obtained  may  be  ascribed  to 
the  insolubility  of  the  gases  in  benzene.  These  results  may  be  easi- 
ly understood  if  we  admit  the  products  of  the  organo-metallic  com- 
pound alluded  too.  For  example  in  case  of  phenol,  the  CH>-Al2Cl5 
combines  v/ith  oxygen  to  form  the  phenate  of  AlgClg,  which  is  decom- 
posed by  water  v/ith  liberation  of  phenol,  thusi- 


So  it  is  evident  here  that  aluminium  chloride  does  not  induce 
the  reaction  by  its  mere  presence.  The  connection  betv/een  the  hydro- 
carbon and  the  chlorine  compound  as  made  by  one  giving  up  the  h^'^dro- 
gen  and  the  other  giving  up  its  chlorine  with  formation  of  hydro- 
chloric acid  similar  to  this  is  the  reaction  of  Grignard  reagent 
with  oxygen. 


The  action  of  the  compound  d^-AlgClg  should  be  analogous  to 
that  of  triphenyl  aluminium®.  The  la.tter  v/as  prepared  by  action  of 
alufninium  on  diphenyl  mercury  and  gives  with  benzyl  chloride,  di- 


' phenyl  methane;  with  oxygen,  phenol;  and  with  sulphur,  phenyl  mer- 
I captan;  but  has  no  action  on  halogen  substituted  in  benzene  ring. 


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5 

Hence,  a well  known  organo-metalllc  compound  gives  the  same  reaction 
as  aluminium  chloride  and  benzene* 

Zinc  ethyl  is  known  to  break  up  by  heating  into  ethylene  and 
ethane.  Here  again  the  analogy  holds good;  for  hydrocarbons  heated 
with  aluminium  chloride  break  up  into  single  saturated  compoimds, 
which  are  easily  isolated,  and  into  complex  unsaturated  compounds# 

No  conclusive  proof  of  the  intermediate  compound  was  advanced  al- 
though certain  experiments  carried  out  in  the  course  of  the  research 
seemed  to  indicate  its  formation  in  small  quantities.  The  evidence 
is  scanty  and  inconclusive# 


The  equation  representing  the  formation  of  an  aromatic  hydrocar- 
bon would  represent  aluminium  chloride  as  a true  catalyst.  In  prac- 
tise, however,  this  is  not  found  to  be  the  case  in  preparing  deriva- 
tives containing  oxygen.  For  in  certain  reactions  it  is  foimd  that 
the  amount  of  product  increases  proportionally  with  the  amount  of 
aluminium  chloride  present# 


^0  RH 

R-C  + AlgCle  = (RCoCl)^  AlgCle  = (RCoR)a  AlgCls  + HCl 

Cl 

, - .,0  HaO 

(R“*C  )a  AI3CI0  —■  R— + AI2CI0 
R R 


' As  Steele'’’  has  pointed  out,  this  does  not  necessarily  preclude 

the  action  of  aluminium  chloride  as  a catalyst,  providing  it  can  be 

I 

i shown  that  it  forms  a stable  compound  with  the  products  of  the  re- 
; action.  The  observation  of  Gustavson®  and  other  seem  to  point  in 
’ this  direction.  A niimber  of  definite  products  have  been  isolated 


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6 

which  seem  to  act  as  catalyst  for  example;  Al2Cl66(CeH0 ) and  ethyl 
chloride  gives  AlgCleCeHs ( )3  6 

Steele  concluded  that  the  action  of  alimiinium  chloride  in  induc- 
ing the  Friedel  and  Crafts*  reaction  differs  from  many  cases  of  a 
true  catalyst  only  in  accident  that  these  reagents  combine  with  cer- 
tain substances  produced  during  the  reaction  and  are  thus  removed 
from  the  system. 


In  rather  recent  research  carried  out  under  supervision  of  Dr. 
Oliver  Kamm®  it  was  found  that  v/hen  benzene  was  refluxed  with  alu- 
minium chloride  very  little  hydrochloric  acid  is  given  off. 


a 


A^AICIs 
AlClg  = 1 [ 


-Cl 


= ^AlCl; 


+ HCl 


They  assume  that  aluminiuia  chloride  adds  to  a double  bond  in  the 

^CH 

benzene  ring  to  form  CH.  7 pAlClg  , and  this  compound  then 

^CH  CH  ^ 

breaks  down  to  give  •d>AlCla  and  hydrochloric  acid.  Further  evi- 
dence in  support  of  this  theory  may  be  cited  by  production  of  phenol 
by  passing  oxygen  or  air  into  a mixture  of  aluminium  chloride  and 
benzene . 

Oa 


HaO 


The  fact  that  some  chlorination  products  are  actually  obtained 
as  evidence  in  favor  of  the  above  mechanism.  In  all  of  these  reac- 


\ 


I 


.) 


^4 


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AMkdr  '' 


7 


fcions  it  was  found  that  the  yields  vrene  proportional  to  the  amount  of 
aluminium  chloride  used  in  proportion  to  the  other  reagents. 

So  far  tv/o  theories  have  been  advanced  to  explain  how  aluminium 
chloride  induces  the  Friede?,  ejid  Crafts*  reaction  and  have  been  dis- 
cussed in  proceeding  pages.  It  v/as  first  maintained  that  the  action 
cf  aluminium  chloride  was  that  of  a catalyst  and  second  it  is  clairaed 
bhat  the  aluminium  chloride  takes  part  in  the  reaction  and  is  used 
proportionally. 


Experimental  facts  favor  the  view  that  <I>Al2Cl^  or  <H>AlCl2 
Is  formed  in  case  of  the  hydrocarbon  derivatives  as  v/ell  as  in  the 


oxygen  derivatives.  If  benzene  and  aluminium  chloride  a.re  treated 

nrith  ethylene  the  resulting  product  is  ethyl  benzene^®, 

A H H HCl 

f )^A1  C = = /V-  C - C - Aids  = ) ) 

^C1  Ij  H H V +AlCls 


Ulso  it  has  been  shown  by  Gustavs on^^  that  normal  propyl  bromide  with 
oenzene  in  the  presence  of  aluminium  chloride  gives  isopropyl  benzene, 
Ikewlse  isopropyl  bromide  with  benzene  presence  of  aluminium  chloride 
Srield  isopropyl  benzene.  The  reaction  may  be  explained  by  the  fact 
hat  if  either  Isopropyl  bromide  or  normal  propyl  bromide  is  tree.ted 
vith  aluminium  chloride  the  same  unsaturated  propyl  compound  v/ill  be 
cbtained.  The  double  bond  breaks  and  the  phenyl  aluminium  chloride 


H H 


adds  in  according  to  Markonnikoff s rule,  -C-^-AlCl 


A ^ 

/y-AlCla  + CHa  - C = 


H 


H _ 

H 


HCl 


■ — CHa 
\GHa 


Likewise  isobutyl  chloride  and  benzene  in  presence  of  aluminium 
chloride  give  tertiary  butyl  benzene. 


8 


In  case  of  the  oxygen  derivatives  the  similar  addition  to  the 
double  bond  takes  place#  If  phenyl  aluminium  chloride  is  treated 
with  acetyl  chloride  the  corresponding  ketone  can  be  obtained  by 
splitting  down  v/ith  v/ater# 


In  order  to  test  out  the  above  hypothesis  an  attempt  to  prepare 
a compound  of  this  natiire,  CgHsAlCla  v/as  carried  out  in  the  following 
manner.  One  mole  of  aluminium  chloride  or  bromide  v/as  treated  with 
one  mole  of  phenyl  magnesium  bromide  under  certain  conditions  speci- 
fied in  the  experimental  part.  Since  chlorbenzene  will  not  react  with 
magnesium  In  anhydrous  ether  it  was  necessary  to  use  the  phenyl 
bromide.  Then  it  was  necessary  to  prepare  aluminium  bromide  in  order 
to  have  the  compound  contain  one  halogen  instead  of  a mixture  of 
halogens.  The  product  obtained  from  the  reaction  of  phenyl  magnesium 
bromide  and  aluminium  bromide  xms  treated  with  acetyl  chloride  and 
then  decomposed  with  water  and  the  resulting  compound  was  aceto- 
phenone, which  is  evidence  in  favor  of  the  above  mechanism.  This  is 
as  far  as  the  reactions  were  carried,  on  accoimt  of  the  fact  that 
the  time  was  limited  and  the  compounds  were  very  unstable  and  diffi- 
cult to  isolate  and  pui‘ify. 


Cl 


Ill 


9 


EXPERIMENTAL 


1.  Apparatus . 

The  setup  of  the  apparatus  in  case  of  preparing  the  organic 
aluminium  compounds  was  identical  in  all  cases#  A three  neck  flask 
was  fitted  v/ith  a mercury  sealed  glass  stirrer  placed  in  the  mouth  of 
the  flask.  One  of  the  necks  was  fitted  vdth  a long  condenser  and  the 
other  neck  of  flask  was  fitted  with  a separating  funnel  and  a tube 
for  passing  nitrogen  into  the  flask#  Figure  I shows  the  setup  com- 
plete • 

The  setup  for  the  preparation  of  aluminium  bromide  consists  of 
a romd  bottom  flask  connected  with  a reflux  condenser  and  a sepatory 
funnel#  The  top  of  the  inverted  condenser  is  fitted  with  a cork  and 
glass  tubing  which  leads  into  a flat  bottom  wide  mouthed  bottle, 
which  also  contains  an  inverted  condenser  with  the  upper  end  closed 
with  a calcium  chloride  tube#  Figure  II  shows  the  setup  as  it  was 
used# 

The  products  were  dried  in  an  atmosphere  of  nitrogen#  The  ap- 
paratus used  consisted  of  a tall  cylindrical  can,  in  the  centre  of 
which  v/as  cut  a large  hole#  A large  rubber  stopper  fitted  with  a 
large  hard  glass  test  tube  was  fitted  in  the  hole  and  made  water 
tight#  The  test  tube  was  fitted  v/ith  a tv/o  hole  rubber  stopper#  In 

one  hole  a tube  was  placed  v/hich  was  connected  to  the  vacuum;  in  the 

nigrogen  tank 

other  hole  a stopcock  was  placed  v/hich  v/as  connected  up  v/ith  and 
the  desired  temperature  was  maintained  by  use  of  a flame#  The  tem- 
perature was  regulated  by  a theroraeter  placed  on  top  of  the  water 
bath. 


I 


16  'U’-1  r ' 1 . *]  T'  V; 

/j-r  ‘ 'jC'? '!■  w-'f'r'o c)  :f.t 


T!'Pj‘  ''  i'. 


,1  ol-I’  ' v^:i' 

fyiff  Dit;  '1.'^  -.■■r ; 


< •' 


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— * 

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& 

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c ' or:!  •'• 

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''r 


■v.« 


iM  fMr: 


Pig.l 


Fig. 2 


10 


A vacuiHn  filter  was  set  up  which  cnonsisted  of  a filter  flask 
with  a large  round  glass  funnel  placed  in  the  neck  of  the  flask*  In- 
side of  the  funnel,  a Buchner  funnel  was  held  tight  by  means  of  a 
cork.  The  top  of  the  round  glass  funnel  was  covered  by  the  top  of  a 
desiccator  which  had  an  opening  in  the  center,  th_rough  which  the  pro- 
duct and  the  nitrogen  could  be  admitted. 

2.  Preparation  of  Reagents . 

PROPYL  MAGNESIUM  BROMIDE 

Place  in  a one  liter  flask  one  mole  of  magnesium  scrap,  add  a 
crystal  of  iodine  and  450  cc.  of  anhydrous  ether.  Fit  the  mouth  of 
the  flask  with  a tv/o  hole  stopper.  Through  one  hole  place  the  end 
of  a condenser  in  a vertical  condition  and  through  the  other  hole  a 
separatory  funnel  is  placed.  Then  add  one  mole  of  propyl  bromide 
drop  by  drop  by  means  of  a separatory  funnel.  If  the  reaction  fails 
to  start,  place  a small  amount  of  the  above  mentioned  constituents  in 
a test  tube  and  heat  until  reaction  has  started  and  then  pour  in  the 
one  liter  fla.sk.  If  the  reaction  becomes  too  vigorous  it  may  be 
slowed  by  applying  a pan  of  ice  to  the  bottom  of  the  flask.  After 
all  the  propyl  bromide  has  been  added  and  the  reaction  ceases,  re- 
flux for  one  hour  and  then  allow  to  cool.  If  magnesium  propyl  bro- 
mide separates,  add  more  dry  ether  in  sufficient  amount  to  keep  it 
in  solution.  Moisted  air  can  be  kept  from  coming  in  contact  with 
Grignard  reagent  by  placing  a calciLim  chloride  tube  on  top  of  the 
condenser  during  the  reaction. 

PHENYL  M AGNES  lUl^  BROMIDE 


Phenyl  magnesium  bromide  is  prepared  by  exactly  the  sam.e  manner 


f 


' t'. 


i /{.’.•Jr**:?  '.1.!/  »'  .r.'JW-  *v  .’i'.! 

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jiii  ui'i'T 


11 


as  propyl  magnesiiim  bromide,  brom-benzene  being  substituted  for 
propyl  bromide,  while  the  other  constituents  are  the  same.  This  re- 
action is  a little  harder  to  get  started  but  this  may  be  accomplished 
with  ease  if  the  ether  in  the  flask  is  kept  boiling  for  ten  or  fif- 
teen minutes  while  the  phenyl  bromide  is  being  added, 

DRY  PSTROLEim  ETHER 

o 

Petroleum  ether  v/as  distilled  and  the  70-80  boiling  fraction 
was  collected.  This  fraction  was  placed  in  a separatory  funnel  and 
shaken  well  with  concentrated  sulph-uric  acid.  After  shaking  the 
liquid  was  allowed  to  stand  and  the  concentrated  sulph-uric  acid  was 
drawn  off.  This  v/ashing  was  repeated  several  times.  In  this  way 
the  unsaturated  hydrocarbons  can  be  removed.  The  petroleum  ether 
was  next  shaken  vdth  water  to  remove  all  acid  and  the  water  was  re- 
moved by  allowing  the  petroleum  ether  to  stand  for  twenty  four  hours 
with  Gael 2.  The  liquid  was  then  poured  off  the  CaClg  into  a distil- 
ling flask  containing  sodium,  which  removed  the  last  traces  of  water. 
The  liquid  was  then  distilled  and  the  collected  in  a bottle, 

ALUI^INIUM  BROMIDE 

The  preparation  of  aluminium  bromide  proved  to  be  rather  diffi- 
cult and  many  attempts  were  made  before  a successful  means  of  obtain- 
ing it  v/as  found, 

A distilling  flask  was  placed  on  an  oil  bath  and  connected  to  a 
combustion  tube  which  was  drav/n  out  at  the  end  nearest  the  flask  and 
slightly  bent  at  the  other  end.  In  the  top  of  the  distilling  bulb  a 
dropping  funnel  was  placed  and  filled  with  bromine.  The  aluminium 


' ‘mD  r.:'- 

. ■,’a: 

. • ,y, ' r-L*". 


f •« 


ii-fu  . ..y  .;  >•  .■  rf  -•  • .V .;» . or^;-  .*:?;•  -jt.  •'iO/’-tp  '• 

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» •>. . . 


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'S 


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/'  ' X''..' o '‘f/i'i'i '■;-'V=  ..'0  0^  i''0;Ov' 7.i^;O\0jfcP'i7  f. 


12 


strips  which  were  previously  washed  with  alkali,  water,  alcohol  and 
ether  were  placed  in  the  combustion  tube  and  the  tube  heated  to  al- 
most red  heat.  Then  bromine  was  dropped  into  the  empty  hot  flask 
and  in  this  way  the  bromine  was  vaporized  and  passed  over  the  alumini- 
um. The  alumini\im  bromide  vapors  were  condensed  in  a flask  at  the 
other  end  which  was  water  cooled  and  which  had  an  outlet  for  excess 
bromine  vapors. 

If  bromine  was  added  to  the  flask  slowly  the  vapors  were  not 
forced  over  into  the  combustion  tube  and  if  it  was  added  fast  enough 
to  cause  the  vapors  to  pass  over,  the  reaction  was  too  violent  and 
the  prod-uct  could  not  be  condensed.  So  in  order  to  carry  the  bromine 
over  and  still  have  a slow  reaction  it  was  necessary  to  have  a gas 
passing  through  the  system  to  carry  bromine  over.  Anything  which  con- 
tains oxygen  could  not  be  used  so  nitrogen  was  tried.  This  did  not 

prove  successful  because  at  the  temperature  to  which  the  aluminium 

it 

must  be  heated  in  order  to  make  it  react  with  bromine, was  also  high 
enough  to  cause  it  to  unite  with  nitrogen  to  form  nitride.^ 

The  next  step  to  simplify  the  process  was  to  insert  a stop-cock 
in  betv/een  the  flask  and  combustion  tube  and  in  this  manner  allow  the 
bromine  to  pass  over  only  when  desired.  The  flask  was  protected  with 
a safety  valve  so  that  when  the  pressure  became  too  great  in  the  flask 
the  cork  would  come  out,  in  this  way  reduce  the  pressure.  This  scheme 
worked  better  than  any  previously  tried  but  it  was  too  difficult  to 
regulate  the  temperature  in  the  laboratory  by  means  of  flames.  It 
probably  would  have  been  satisfactory  method  in  an  electric  furnace, 
where  a constant  temper atin^e  could  be  maintained. 


13 


The  next  attempt  to  make  alumini-um  bromide  was  by  bromination  of 
aluminium  strips  in  the  presence  of  carbon  tetrachloride.  This  did 
not  prove  to  be  satisfactory  and  also  using  ether  as  a solvent  did 
lot  help# 

Finally  aluminium  was  placed  in  dry  ether  and  dry  hydrobromic 
acid  was  allowed  to  pass  through  the  solvent.  After  the  solvent  be- 
came saturated  the  hydrobromic  acid  began  to  eat  up  the  aluminium  and 
lydrogen  was  evolved.  The  aluminium  as  it  passed  into  solution  formed 
a heavy  oily  liquid  which  separated  from  the  ether.  The  dry  hydro- 
Dromic  acid  was  made  by  placing  benzene  and  ion  fillings  in  the  flask 
in  Figure  II  and  dropping  bromine  into  it. 

The  oily  layer  which  contains  the  aluminiimi  bromide  was  subjected 
to  a current  of  dry  air  \mtil  all  the  hydrobromic  acid  had  been  ex- 
pelled and  then  washed  with  anhydrous  ether  and  evaporated  to  dry- 
ness, three  or  four  times  and  in  this  v/ay  a nice  solid  product  was 
obtained.  The  yield  of  pure  anhydrous  aluminium  bromide  is  95  per 
cent, 

3,  Ac ti on  of  Grignard’s  Reagent  on  Aluminium  Chloride  and  Bromide, 
PROPYL  MAGNESIUM  BROMIDE  AND  ALUMINIUM!  CHLORIDE 

My  first  attempt  was  to  prepare  tripropyl  aluminium.  Three  moles 
of  propyl  magnesium  bromide  were  placed  in  the  flask  shown  in  Figure  I 
and  a little  of  the  aluminium  chloride  added  slowly  to  it,  through  the 
neck  of  the  flask.  Nitrogen  was  also  allowed  to  pass  slowly  through 
the  solution  in  the  flask  in  order  to  have  an  inert  atmosphere.  The 
stirrer  v/as  then  started  and  the  rest  of  the  mole  of  aluminium  chlor- 


v.>-  - ••  -• 


',  *lo  f ■' 

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I 

/ iva’t;:.'-'  wtiTi 

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j r o-a;:  X . n:  u ■■•n-.f'r  m 
iv  'A  ->  f "V  lj  . f-’  oO  ' ..1  '■■■■■X,'- 
' ,'S  •■•nX  ; --V  ' ■ ' ' a 

, nr":  * ■-  ;■ 

ii 


*A',*y.au)«i3g'  T 


14 


ide  was  added  slowly.  A violent  reaction  took  place  with  the  forma- 
tion of  a solid  mass  in  the  bottom  of  the  flask.  The  heat  of  reac- 
tion was  so  great  that  most  all  the  ether  was  lost  and  a gray  clay 
like  mass  was  left  in  the  bottom.  This  solid  was  not  deccxnposed  by 
water  but  acid  decomposed  it  very  rapidly. 

In  the  next  run  the  aluminium  chloride  was  added  more  slowly  and 
at  the  same  time  the  flask  was  kept  in  an  ice  bath  after  the  reaction 
had  ceased  it  was  refluxed  for  fifteen  to  twenty  hours  and  at  the 

end  of  this  time  it  v/as  distilled  under  pressiu’e  of  190  mm., but  no- 

o 

thing  came  over  above  55  . The  reaction  expected  was  as  follov/s: 

/Br 

3 CgH,^  MgBr  + AlClg  = (GgH7)Al  + 3 Mg 

Cl 

In  case  of  alkyl  mercury  com.pounds  it  has  been  found  that  it  re- 
quired a much  higher  temperature  and  a longer  time  to  attach  the  sec- 
ond alkyl  group  to  mercury  than  it  does  the  first  alkyl  group.  So  it 
seemed  logical  it  would  apply  likewise  to  aluminium  compounds  of  this 
nature.  And  since  the  alkyl  groups  must  be  linked  to  aluminium  dis- 
placing three  chlorine  atoms  it  seemed  as  thou^  it  v/ould  require  a 
longer  time  and  a much  higher  temperature  to  place  the  second  and 

third  alkyl  groups  onto  aluminium.  So  a higher  boiling  substance  was 

o 

used  in  place  of  dry  ethyl  ether.  Dry  petroleum  ether,  b.p.  70-80  , 
were  used.  The  propyl  magnesium  bromide  was  made  in  exactly  the  same 
way  as  described  for  propyl  magnesium  bromide.  In  this  case  the 
Grignard  reagent  was  not  soluble  in  dry  petroleum  ether  and  dimethyl 
aniline  was  used  as  catalyst  instead  of  iodine. 

The  propyl  magnesium  bromide  suspended  in  petroleum  ether  solu- 
tion was  treated  in  the  same  manner  as  described  in  the  first  run. 


15 


After  all  the  aluminiijm  chloride  had  been  added  it  was  allowed  to  re- 
flux for  thirty- six  hours  and  then  cooled,  transferred  to  distilling 
flask  and  distilled.  The  petroleum  ether  was  driven  off  and  as  the 
temperature  was  increased  the  dark  brown  oily  liquid  began  to  decom- 
pose, A solid  similar  to  the  one  in  the  first  case  was  found  in  the 
bottom  of  the  flask. 

In  order  to  get  around  the  formation  of  the  undesirable  mass  in 
the  bottom  of  the  flask  a new  method  of  procedure  was  tried.  This 
time  the  aluminium  chloride  was  dissolved  in  dry  ether  and  placed  on 
the  3-neck  round  bottom  flask.  The  stirrer  was  started  and  nitrogen 
was  passed  through  several  minutes  to  expell  all  the  air.  Then  3 
moles  of  propyl  magnesium  bromide  was  added  slov/ly  to  the  one  mole  of 
alimninium  chloride,  dissolved  in  the  dry  ether.  After  the  reaction 
had  stopped  the  stirring  was  continued  and  the  liquid  v/as  refluxed 
for  thirty  minutes,  A solid  was  formed  on  the  bottom  of  the  fld'sk 
which  contained  light  brov/n  crystals  and  also  some  propyl  magnesium 
bromide • 

In  similar  manner  the  above  reaction  was  run  and  instead  of  3 
moles  of  CgHfj-MgBr  one  mole  was  used.  The  time  of  reflux  this  time 
was  increased  to  thirty-six  hours.  A nice  li^t  yellow  crystalline 
solid  separated  out  in  the  bottom  of  the  flask.  This  was  filtered 
by  means  of  the  filter  described  in  the  first  part  of  this  article 
and  sealed  in  a glass  stoppered  bottle. 

The  compound  then  obtained  burned  readily  and  the  residue  con- 
tained aluminium.  It  was  easily  decomposed  by  moisture.  By  blo?/ing 
one’s  breath  upon  the  compound  hydrolsis  would  take  place.  On  adding 


'i-K  € 


hoi.i-H  rxt-1^'  .'•'  .fCv-i'"’ 


Cl  , 


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16 

water  to  a little  to  it  in  a test  tube  a gas  was  given  off  which 
burned  readily, 

A ,2000  gram  sample  was  heated  v/ith  water  and  the  gas  collected. 
The  number  of  cc,  given  off  by  this  sample  was  36,  which  indicated 
that  one  propyl  group  had  replaced  a chlorine  group  in  the  alu:-iiiniura 
chloride , 

Br 

CsH^MgBr  + Aids  > C3H7AICI2  + Mg  ^ 

Cl 
2O 

GqEq  + AlClgOH 

This  compound  was  not  analyzed  because  of  the  mixture  of  alumini- 
um halogens  which  would  naturally  be  present  in  the  molecule.  Also 
no  solvent  could  be  found  which  would  dissolve  it  and  therefore 
could  not  be  purified, 

ACTION  OP  PHENYL  MAGNSSIUJ/i  BROMIDE  ON  ALUMINIIB'I  CHLORIDE 

Phenyl  magnesium  brom-ide  was  prepared  by  the  method  previously 
described.  Then  aluminium  chloride  was  dissolved  in  an  excess  of  an- 
hydrous ether  and  poured  into  the  three  neck  flask.  The  stirrer  was 
started  and  the  phenyl  magnesium  bromide  was  added  slowly  with  con- 
tinuous stirring.  The  reaction  was  fast  and  a great  deal  of  heat  was 
evolved  as  a steady  stream  of  ether  ran  back  from  the  condenser. 

After  the  three  moles  of  phenyl  magnesium  bromide  had  been  added  the 
liquid  was  allowed  to  reflux  for  fifteen  to  sixteen  ho\irs  v/ith  a 
stream  of  nitrogen  bubbling  through  the  constantly  stirred  mixture. 
The  nitrogen  was  previously  dried  by  passing  it  through  sulphuric 
acid. 


17 


After  refluxing,  the  flask  v/as  allowed  to  cool  and  the  contents 
of  the  flask  were  placed  in  a vacuum  desiccator  and  ether  allowed  to 
evaporate  off.  There  remained  in  the  dish  after  evaporation  a dark 
brown  solid  covered  with  a oily  brovm  liquid  which  could  not  be  evap- 
orated by  means  of  the  vacuum  and  which  also  decomposed  on  heating. 
The  contents  of  the  dish  was  placed  in  the  vacuum  filter  and  dried  as 
completely  as  possible  in  this  manner. 

Qualitative  tests  were  then  performed  on  the  solid.  It  burned 
readily  when  placed  on  the  end  of  a spatula  and  subjected  to  the 
flame,  giving  a sooty  black  flame.  A little  was  next  fused  with  so- 
dium. and  tested  with  silver  nitrate  for  halogens  and  it  gave  a test 
for  both  bromine  and  chlorine. 

The  next  step  was  to  find  a solvent  so  that  it  might  be  recrys- 
tallized and  purified.  On  adding  water  or  acids  it  was  foimd  that 
hydrolysis  took  place  very  rapidly  in  the  cold.  On  the  top  of  the 
water  was  a yellow  layer  which  had  an  odor  like  benzene.  The  yellow 
layer  was  separated  from  the  water  and  aluminium  hydroxide  and  a meta 
dinitro  derivative  was  made  by  treating  the  liquid  with  a mixture  of 
nitric  acid  and  sulphuric  acid.  A white  solid  was  precipitated  out 
and  this  v/as  allov/ed  to  dry  and  a melting  point  taken.  It  corre- 
sponded to  the  melting  point  for  meta  dinitro  benzene  given  in  the 

o 

literature  ra.p,  90  /o.  A.lcohol  also  failed  as  a solvent  because  hy- 
drolysis again  took  place  but  this  time  more  slowly.  On  trying  ether 
as  a solvent  the  only  layer  was  produced  and  this  therefore  could  not 
be  used  to  an  advantage  as  a solvent.  The  product  was  also  insoluble 
in  carbon  tetrachloride,  ligroin,  acetone,  toluene,  chloroform. 


18 


anisol  and  only  very  slightly  soluble  in  benzene.  Carbon  bisulphide 
also  failed  to  have  any  dissolving  action  on  the  product,  so  a good 
solvent  for  the  compound  could  not  be  found.  Benzene  proved  to  be 
the  best  solvent.  By  several  extractions  with  boiling  benzene,  some 
of  the  product  could  be  obtained  but  it  was  not  pure. 

A few  reactions  were  tried  with  the  brown  crystalline  product.  A 
little  of  the  compound  was  placed  in  a flask  and  refluxed  with  excess 
of  ethyl  bromide  for  three  hours.  The  object  was  to  test  the  theory 
and  see  if  any  ethyl  benzene  could  be  produced.  But  on  examination 


of  the  contents  of  the  flask  there  was  no  ethyl  benzene  formed*  ?/hen 
this  run  was  mad.e  no  hydrochloric  acid  gas  was  passed  into  the  solu- 
tion while  the  mixture  was  refluxing  and  this  may  account  for  the 
failure  to  obtain  the  ethyl  benzene,  because  when  ethyl  benzene  is 
made  by  using  ethyl  bromide,  benzene,  and  aluminium  chloride  by  the 
Friedel  and  Grafts’  reaction  an  atmosphere  of  hydrochloric  acid  gas 
is  present. 

Another  portion  of  the  product  v/as  treated  with  acetyl  chloride 
and  the  reaction  was  very  vigorous.  A solid  product  was  found  in  the 
bottom  of  the  flask.  The  solid  product  was  readily  hydrolyzed  by 
water  in  the  cold  with  the  formation  of  a yellow  layer  on  the 
top  of  the  water,  v/hich  had  the  characteristic  odor  of  acetophenone. 
The  layer  was  drawn  off  and  treated  with  phenyl  hydrazine.  A white 


precipitate  was  produced  which  melted  at  104  . The  melting  point  of 


o 


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19 

o 

the  phenyl  hydrazine  of  acetophenone  given  in  the  literature  as  103  • 
In  similar  manner  the  compound  was  treated  with  benzoyl  chloride  and 
then  with  water.  It  gave  a very  characteristic  odor  of  benzophenone , 


A quantitative  analysis  was  not  run  on  this  compound  because  of  the 
fact  that  it  could  not  be  obtained  pure  and  also  because  a mixture  of 
halogen  was  present  and  a true  analysis  could  not  be  obtained.  Either 
of  the  compounds  shown  in  the  equation  might  be  present  or  even  a 
mixture  of  the  two.  So  the  next  step  necessary  in  order  to  have  a 

. Br 


■MgBr 


Ether 


+ AICI3 


0“ 


\ 


Cl 


Al-Cl 

\ 

Cl 

uniform  compound  was  to  use  aluminium  bromide  instead  of  aluminium 
chloride.  Since  aromatic  chlorine  compounds  will  not  react  with 
magnesium  in  dry  ether, 

ACTION  OF  PHENYL  MAGNESIA  BROMIDE  ON  ALUMINIIB!  BROMIDE 


One  mole  of  aluminium  bromide  prepared  as  described  previously 
, containing 

was  placed  in  a three  neck  flask  /\  anhydrous  ether.  Three  moles  of 
phenyl  magnesium  bromide  were  added  slowly  to  the  aluminium  bromide. 
The  phenylraagnesium  bromide  must  be  added  slowly  and  with  constant 


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♦r^r' 


20 


stirring  because  the  heat  produced  causes  a constant  stream  of  ether 
to  flow  dovm  the  condenser  and  this  will  escape  at  the  top  if  reac- 
tion is  allowed  to  run  too  fast.  On  adding  the  phenyl  magnesium 
bromide  the  color  of  the  solution  was  first  orange  and  then  it  chang- 
ed to  white  and  finally  to  a dark  brown  color.  The  mixture  was  re- 
fluxed for  fifteen  hours  after  all  the  phenyl  magnesium  bromide  had 
been  added  and  then  cooled.  The  ether  was  next  evaporated  off  and 
the  solid  brown  crystallized  product  v/as  obtained  which  had  the  same 
appearance  as  the  one  obtained  when  aluminium  chloride  was  used.  This 
compound  was  as  highly  insoluble  as  the  aluminium  chloride  compounds. 

A little  of  the  compound  was  placed  in  a beaker  and  benzene  was 
added  and  heated  to  boiling.  The  soluble  portion  was  poured  off  and 
more  benzene  added  to  the  beaker  and  this  was  repeated  until  the  ben- 
zene was  perfectly  clear.  The  product  thus  obtained  from  the  benzene 

o 

extract  was  dried  at  100  in  a vacuum  drier.  An  analysis  on  the 
compound  was  carried  out.  The  carbon  did  not  check  with  the  theo- 
retical percentage.  However,  an  analysis  showed  the  presence  of 
aluminium,  magnesium  and  bromine 

In  the  next  run  a different  method  of  procedure  was  adapted. 

One  mole  of  aluminium  bromide  was  placed  in  the  flask  and  one  mole 
of  phenyl  m.agnesiura  bromide  was  added  slowly  and  after  reaction  had 
ceased,  the  mixture  was  refluxed  for  five  hours  and  then  the  second 
mole  of  Grignard's  reagent  was  added  and  likewise  refluxed  for  five 
hours.  At  the  end  of  this  time  the  third  mole  of  Grignard's  reagent 
was  added  and  refluxing  continued  for  five  hours  longer.  The  flask 
was  then  cooled  and  an  excess  of  acetyl  chloride  was  added  slowly 


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21 


with  constant  stirring.  A beautiful  orange  precipitate  settled  down 
to  the  bottom  of  the  flask.  This  product  was  drav/n  off,  filtered  by 
means  of  vacuum  filter,  and  dried  in  the  vacuum  drier# 

An  analysis  was  carried  out  on  this  sample  for  carbons,  halogens, 

and  aluminium  and  the  following  results  were  obtained: 

. o 

.5000  grams  of  substance  gave  148  cc.  of  COg  at  28  and 
748#6  mm.  pressure 

Calc,  for  C,  H,  Al,  Halogen  Oxygen  C = 15.7 

Pound  C = 13.8 

•5000  grams  of  substance  required  50.53  cc . of  AgNOs  which 
was  0981  normal. 

cc . calculated  = 50.9 

cc.  found  =:  50.53 

Aluminium  was  determined  by  heating  .5000  grams  of  substance 
in  crucible  in  open  air  and  the  oxide  was  weired. 

Calculated  for  aluminium  = 9,1 

Pound  =10.8 

In  the  calculation  of  the  theoretical  results  the  formation  of 
the  following  compound  was  used  as  bases: 


This  compound  was  readily  hydrolyzed  by  water  giving  a small  quantity 
of  acetophenone. 

The  final  and  best  method  of  procedure  which  was  found, was  to 
place  one  mole  of  aluminium  bromide  in  the  three  neck  flask  connect 


Cl 


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22 

up  as  indicated  in  Figure  I and  add  slowly  v/ith  constant  stirring 
one  mole  of  phenyl  magnesium  bromide  and  three  portions  to  the  flask 
allowing  the  mixture  to  reflux  for  five  hours  each  time  before  the 
next  portion  was  added.  After  the  three  portions  had  been  added  the 
mixture  refluxed  for  fifteen  hours,  the  flask  was  cooled  and  an  oily 
clear  layer  v/as  in  the  flask.  The  oily  layer  was  drawn  off  and 
placed  in  a flask  fitted  Y/ith  a rubber  stopper.  This  oily  substance 
was  then  shaken  v/ith  carbon  disulphide  and  at  once  the  oily  layer 
formed  a solid  mass  of  brown  crystals  in  the  bottom  of  the  flask. 

The  solid  was  then  shaken  well  v/ith  carbon  disulphide  to  remove  all 
of  excess  alimiinium  bromide.  After  this  treatment  ether  was  added  to 
remove  any  excess  phenyl  magnesium  bromide  and  then  the  solid  v/as 
finally  treated  with  sjiisol  to  remove  any  magnesium  bromide  v/hich 
might  be  present.  After  this  treatment  it  was  again  heated  to  the 
carbon  bisulphide  in  order  to  obtain  again  a good  crystalline  product 
The  carbon  bisulphide  was  removed  by  vacuum  filter  and  then  the  prod- 
uct was  dried  in  a vacuum  drier. 

The  product  hydrolyzed  very  readily  with  v/ater  giving  benzene. 

It  reacted  v/ith  a.cetyl  chloride  giving  acetophenone  on  ana.lysis  it 
showed  the  presence  of  carbon,  aluminium  and  bromine.  It  melted  be- 

o 

tv/een  280-285  • A quantitative  analysis  was  run  on  the  product  and 

o 

it  v/as  found  by  the  total  carbon  method  that  it  contained  26,5  /o 
carbon  which  Indicated  a formula  of  the  follov/ing  structure  dl>  AlClg 
H owever,  on  further  analysis  it  v/as  found  that  the  percentage  alu- 
minium and  bromine  obtained  experimentally  did  not  check  with  this 
formula.  At  this  point  it  occurred  to  the  writer  that  v/hen  the  com- 
pound was  hydrolyzed  by  water  that  ether  was  alv/ays  given  off.  So 


23 


from  this  it  was  concluded  that  one  molecule  of  ether  of  crystalliza- 
tion was  present  and  v/hen  this  v/as  taken  into  consideration  the  alu- 
minium and  bromine  checked  with  the  calculated  amount,  but  the  carbon 
did  not  check  as  the  results  of  analysis  will  show. 


,5000  grams  of  substance  gave 
and  740  mm,  pressure 


cc,  of  COa  at  30 


-AlBr, 


Calculated  for  carbon 
Calculated  for  carbon  O -AlBr2(C2H5 )g0 
Experimental  for  carbon 


= 27.7 

= 35,5 
= 26,3 


,5000  grams  of  substance  gave  ,1087  grams  of  AlgOg 

o 

Calculated  for  aluminium  = 7,98 

Pound  for  aluminium  = 7,5 

.5000  grams  of  substance  required  35,35  cc , of  ,0981  normal 
silver  nitrate 


Calculated  for  bromine 
Found  for  broraine 


= 47.3  7, 

= 47.89°/ 


since  the  bombs  v/hich  were  used  for  making  fusions  contained  no 
gasket  ajfid  also  the  fact  that  ether  might  be  driven  off  before  fusion 
temperature  was  reached,  it  was  thought  that  in  this  way  the  carbon 
of  the  ether  of  crystallization  was  lost.  For  as  it  was  stated  be- 
fore the  carbon  checked  v/ith  the  formula  assumed  without  the  molecule 
of  ether  of  crystallization.  The  carbon  and  hydrogen  was  then  deter- 
mined by  combustion.  The  results  were  as  follows: 

.2000  grams  sample  gave  .2215  grams  of  COg 

Calculated  for  carbon  = 38.5 


Found  for  carbon 


=30.20 


24 


2000  grams  of  substance  gave  .OVIV  grams  of  HgO 
Calculated  for  hydrogen 
Found  for  hydrogen 


= 4.5  / 

' o 

= 4.04  /o 


o 


The  carbon  again  did  not  check  with  the  theoretical  amount, 
which  may  be  due  to  the  fact  that  in  combustion  the  compound  burned 
so  easily  that  the  combustion  ran  to  fast  and  some  carbon  dioxide 
escaped  before  it  could  be  dissolved  and  also  some  of  carbon  dioxide 
might  have  been  carried  out  by  a stream  of  oxygen  which  was  constant- 
ly passed  through  during  combustion.  The  experim.ental  work  was 
closed  at  this  point. 


M- 


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t; 


IV 


25 


CONCLUSION 

The  Grlgnard’s  reagent  reacts  with  aluminium  chloride  and  bromide 
but  the  allcyl  ra.dical  do  not  replace  all  the  chlorine  to  give  the 
tri alkyl  compound* 

Good  evidence  was  obtained  which  indicated  that  phenyl  aluminium 
dibromide  was  formed  when  aluminium  bromide  v/as  treated  with  phenyl 
magnesium  bromide*  The  phenyl  aluminium  dibromide  was  broken  down 
by  water  giving  benzene j it  reacted,  with  acetyl  chloride,  v/hich  v/as 
hyd.rolyzed  by  water  to  give  acetophenone^  it  gave  on  burning  a char- 
acteristic odor  of  phenol* 

9-ryl  aluminium  dichlorides  a.re  solids  which  are  readily 
hydrolyzed  by  water,  acids  and  alcohol  and  consequently  are  very  un- 
stable in  presence  of  air* 

The  behavior  of  phenyl  aluminium,  dibromide  toward  acetyl  chloride 
furnishes  good  evidence  that  a similar  compound  is  formed  as  an  in- 
termediate in  the  Friedel  and  Craft’s  reaction  in  preparation  of  both 
hydrocarbons  and  oxygen  derivatives. 

Anhydrous  aluminium  chloride  or  magnesium  bromide  may  be  easily 
prepared  by  passing  dry  hydrobromic  acid  through  dry  ether  containing 
sm.all  strips  of  these  metals* 


fr,  n ' 


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■'  '1  ••:  ■'  ; I'  ■ m tv j t/J  I 

■ ' . ^ ■ ' 

>,  v^)v  ct.  'tc:‘ -n'  'Vr\h^y:^'So’'\  'ci  '■ 
\ . » * ■ •?:c»  ••to.%'^''.e  •*  | 


>\ 


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V .> 


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'''  n.;AV'?v^<-' 

• JUrd» 

*vV 

i:-  ;*  ''V . o-r!  5 !r*'.\l)i  o*'i:(.!’  !;ij.jfi;'''!'fca;:''>5tv  'to  o. r <i'?  n>.ov;0'‘^X4itA  .,, 


V 


26 


BIBLIOGRAPHY 

1.  B.  S,  Hopkins,  General  Chemistry  of  Rarer  Elements. 

2.  Cohen.  Vol.II,  p.l95. 

3.  Corap.  rend. 86,  pp. 884-7;  Comp,  rend .86,  pp. 1368-71. 

4.  J.  Chera.  Soc.M,  670  (1878). 

5.  J.  Chem.  Soc.M,  792  (1878). 

6.  J.  Chern.  Soc.77,  1006  (1900). 

7.  Steele.  Trans.  Chem.  Soc.83,  1470  (1903). 

8.  Mayo.  Study  of  Priedel  and  Crafts'  Reaction. 

9.  Bull.  Soc.  Chera. 2,  31,  529;  Bull.  Soc.  Chem, 2,  34,  322;  Bull. 

Soc.  Chera,2,  42,  213-216, 

10,  Monatsh.  fiir  chemie  9,  613  (1898). 

11,  Ann,  de  chimie  et  de  phys,(6)  449  (1884);  Ann,  de  chimie  et 

de  phys,(6)  1£,  411  (1887);  Ann.  de  chimie  et  de  phys.(6)  11, 
263  (1887);  Ann  de  chimie  et  de  phys.(6)  lA,  333  (1888), 

12,  Elbs  synthetische  darstellung  methoden,  Vol.II,  p, 140-171. 

13,  Amer,  Chem,  J.^,  365  (1900). 

14,  Rec.  Trans,  chimie  19^,  19  (1900). 

15,  Ber.43,,  3627  (1908). 

16,  Annual  reports  of  progress  of  chemistry  for  1916,  Vol.13,  pp,98 


99. 


